Acyclic hydrazinium chlorides



the .known prior art.

2,929,847 p ACYCLIC THYDRAZINIUM CHLORIDES Bernard Rudner, .Luther O. Young, and Marguerite E. Brooks, Baltimore, Md., assignors to W.R. Grace & 'Co., New York,'N.Y., a corporation of Connecticut No Drawing. Q ApplieatiomFebruary 20,-:1957 ;Serial No. 64 1,271 I W 7 Claims. :1 c1. 2605 583 invention relates'to quaternary nitrogenous salts. In one spec fic aspect, it relates to quaternized derivatives of substituted hydrazines. In still another aspectQit relates tojnovel acyclic hydrazinium chlorides.

Heretofore, uater ary hydrazinium salts have been obtained only on a laboratory scale. A known preparation of these interesting compounds comprises the reaction of 1,1-di-substituted hydrazines with alkylatin'g Because of the extreme agents, e.g., methylchloride.

difficulties involved in preparing the parent hydrazinesi and the limitations vof their final alkylation (see :O.'

Westphal, Berichte der Deutschen Chemisc'hen 'Gesell- 2,929,847? Batented Mar. 22, 1960 2 available a new class of useful hydrazinium chlorides having the general formula:

In the above fontrulaRiszin aliphatic hydrocarbon res'i due having from 16-24'carbonatoms. More specifically it, is an alkyl, alkenyl,or alkadienylvradical having from 16 24 carbon atoms. R and R" areimembers selected from the group consisting of alkyl radicals havingtfrom l to 24 carbon atoms, alkenyl radicals having from 2 to 24 carbon atoms, and alkadienyl radicals having from 4 to 24 carbon atoms.

It; has recently been discovered that chloramine will react with tertiary amines to form tri-substitutcd hydra 1 zinium chlorides. This new reactionpresen'ts practically 1 schaft, 74: 759 et. seq., 1,365 .et. seq. 119.41), only limited-types of hydrazinium chlorides havebeen 'here- 7 I tofore available. Using Westphals method it is obvious I that the preparation of any specific hydrazinium "cation depends on thefavailability of the substituted hydrazine,

as well as the ability of'that substituted hydrazine to undergoalkylation with the necessary alkylxhalide. Among the compounds discovered by Westphal were the trihexyl hydrazinium chloride, the dodecyldimethyl hydrazinium chloride, the hexadecyldimethyldrazinium bromide and hexadecyldimethylhydrazinium iodide. Because of the inherent limitation of his alkylation reaction; Westphal found it impossible to prepare hydrazinium chlorides of greater chain length than the dodecyldimethylliydrazinium salt. He was moresuccessful using methyl bromide and methyl iodide as alkylating agents; however, he did not prepare hydrazinium salts havinga carbonchain longer Q: than 16 carbon atoms since long chain' alkyl substituted hydrazinesare not readily available, the only known compounds of this particular type are those prepared by Westphal." We havediscovered certain homologous and vanalogous acyclic hydrazinium salts which Westp:hal was .unable to prepare directlylby. his method.

Our novel acylic hydraziniumchlorides possess properties limitless possibilities for .;the preparation of novel interesting chemical compounds which, because of their structure and inherent physical properties, have a wide range of uses, Tertiary amines are readily available bases. 'Chlora'n ine is an excellent reagent since it can be economically obtained in commercial quantitiesmby using the. well known process -of ,Harry .H. Sisler et al., describediinUSQBat. 2,710,248 where chlorine and ammonia are reacted in the vapor 'phaseto produce chloramine (monochloramine). Bytreatingaclassof tertiary :a'mines containing. long chain aliphatic residues with chloraminewe have discovered the new generic class' of.

I hydrazinium salts referred to hereabove- I .In preparing the compoundsoflthe present invention it is usually suitable tocontact .chloramine with a solution of the selected tertiary amine, allow the reaction to proceed until the desired quantity ofchloramine is consumed and then isolate and purify the'resultant hydrazinium chloride by, standard laboratory techniques. While,

chloram'ine is most advantageously prepared in the form j i nstance chloramine can be n iadejby reacting chlorine.-

"ivith anexcess vof ammonia' or a gaseous chloramine-ammoniamitrogen stream obtainedgfroin a generator constructed according to the teachings of Sisler et al. other methods are equally adaptable for the purposesot 'th'e present invention, For

bori ,solv'ent under controlled-conditions of mixing at low temperatures. Such a procedure is fully described in US. Patent No. 2,678,258-to1ohn FJ'Haller. ;Another effective procedure is that of Coleman et al., fully described in Inorganic Syntheses, vol.- I, 59, (1939). Aljternatively, thev compoundsof the present inventioncan jbe lmadeldirectly by-the procedure'described .inthe coand utility {which are; completely unobvious in v'iew of l This application is a continuation in part of'ourco-pending applications S.N. 546,784, filed November l'4,'"l95 5, -and S.N.-560;282', filed January 20, 1

1956, both now abandoned.

It is therefore an object of the present invention to provide a new generic class of acyclic hydrazinium chlorides which, because of their unique properties 'andutility, are commercially iacceptablefor purposes beyond the realm of utilitypossessed by 'anyzsimilarprior art compounds I 'In accordance-with the present invention wejhavemade geste'd amines areintended tb be merely illustrative, since flitj is obvious that the jhomologues of these compounds embraced 'by'the general formula setforth above would be, equally applicable in the production of individual s,peciesj o't our new and novel class. V

a alogenated hydrocatthe Rudner method to be apreferrd Methyl-bis-(Z-methylhexadecyl. hydrazinium chloride. Dlmethyl-S-octadecyl 1,1-dln:ethyl-l-(ttoctadecyl) hydrazinium chloride. Dlethyloctndecenyl-7 1,l-diethyl-l-(7-octadecenyl) hydrazinlum chlor e. Decylethyloctadecyl 1-decyl-l-ethyl-l-octadecyl hydrazin- Ethylbls'(7,10-octndecadicnyl) Dlmethyl(2,4,4,6,6,8,8 heptamethylnonyl-2.

Diethylelcosyl r e. 1m ethyl-1,1-bis-(2-methylhexadecyl) luro chloride. l-ethyl-l-ht 7,10cctadecadlenyl) hydrazinium chloride;

-Trloctadecyl 1,1.i1dmoctadecyl hydrazinium ;chlor e. 1 Dlmetbylnonsdecyl l,1-ld]imedthyl-1-nonadccyl hydrazinium c.0r1 c. I l

Methylrmdecylnonadecyl l-methyl-l-nonatlecyl-l-undccyl hydrarlnlum chloride. 1,1dirnethyl-l-(2,4,4,6,6,8,8heptamethylnonyl-2) hydrazinium chlo- (4,6,8,10,l2,14-hexamethylpentadecyl-2-)dlmethyl. nllliithlylpentadecylaj hydrazinium c or e. Dlethylbrassidyl 1, lilrlileitdh yl-l-brassldyl hydrazinium c or e.

Dlethylerucyl Llfitcthyl-l-erucyl hydrazinium chlor e. Y

Dtmethyl(2,4,4 6,6,8,8,10,10,12, 1,l-dlmethyl-l-(2,4,4,6,6,8,8,10,10,12,12

12 undecamethyltrldecyl-a). undecamethyltrtdecyl-2-) hydrazintum chloride. c Dl-n-propyltetracosanyl 1,l-dl-n-propyligtetracosanyl .hydrazlntum chlor e.

As well as the individual amines of the type shown 'hereabove in Table 1 there are available, for the purposes of preparing compounds of. the present invention,

commercial mixtures of such tertiary amines. From these mixtures are preparedthe soya, coco and -hydrotallow hydrazinium chlorides and similar products. These amine mixtures contain alkyl radicals of varying chain length which vary also in degrees of un- 5 saturation. They .will be fully described in termsof the specifications made available by their manufacturers in 'the examples which appear infra.

In, discussing the several methods by which chloramine may be made available for reaction with the tertiary amine, we indicated that the choice of reaction medium :could be varied extensively. We have successfully obtained our compounds by conducting the reaction of c hloramine and the appropriate tertiary amine in anhydr'ous solution using as a solvent either an excess of the :reactant amine oran unreactive organic liquid. The reaction may also be carried out in aqueous solution if .such conditions appear to be preferable. reactive, as applied to the organic liquid solvent, is intended to embrace those solvents that do not, react The term unpreferentially with chloramine, ammonia or the reactant amine under the conditions employed. It is obvious, therefore, that the choice of solventis one of economy and simplicity.v For good absorption (and therefore reaction) it may be desirable to bubble chloramine through {a long column of, a solution comprising the tertiary amine "dissolved in a relatively cheap inert solvent. Solvents which serve this purpose include hydrocarbons, e.g., heptane, cycloh'ex'ane, benzene, xylene and the like; others, "e.gl, diethyl ether, diamyl ether, dioxane and anisole', ,amides, e.g., dimethyl formamide and dimethylacetamide;

:halohydrocarbons, e.g., chloroform, carbon tetrachloride, trichlorethylene and .trichlorbeniene; and nitroaromatics, eJg. nitrobenzenei For special purposes water and other .hydroxcyclic' solvent uch as ethanol and-Cellosolve may 'b,e us'ed.

The unobviou's'properties and utility or at. n v corn;

pounds will be fully apparent from the commercial evalor a measurable extent these desirable properties. Furthernation data which appears in the working examples. However, a few general comments are appropriate at this point. Our novel compounds show astonishing utility in the textile industry. No known hydrazinium salts are useful for such purposes.

As one facet of their utility in the textile field, our compounds have considerable surface activity which helps to make them excellent detergents and softening agents. Generally speaking, many fibers, including those textiles destined for use in garments or household applications (e.g., sheets, pillow cases, bed spreads, drapes, etc.) are finished with some type of softening agent. Softening is necessary to counteract the inherent harshncss present in most textile fibers, and the added harshness caused by mechanical processing. Most types of softening agents. possess a'somewhat similar chemical structure. Ordinarily they comprise a molecule made up of a hydrophobic or lipophilic group, often derived from a long chain alkyl source, and a solubilizing or hydrophilic group. The hydrophilic group may be a quaternary structure v(such as is characteristic of our novel compounds).

Softness (or hand, as it is known in the textile trade) can be effectively imparted to most fabrics by treating themrwith a water dispersion of any of our novel salts. A treating bath comprising 0.1 to 4% by weight of softener solids, based on the weight of cloth, and a total water volume equivalent to twenty times the weight of the fabric is suflicient for'this purpose. The bath is preheated to a temperature of 'll5-120 F. The fabric is placed in the bath and agitated for a short period of time during which the softener exhausts from the bath onto the fabric. The fabric is subsequently dried and steam pressed. I

As softeners our compounds are equal or superior to the competitive commercially available materials in the field. One of them, a mixture of hydrazinium salts containing chiefly methylbisoctadecylhydrazinium chloride, is more effective than any known standard softening agent for'treating rayon or Orlon. Table 2 is illustrative of the astonishing effectiveness of this'novel compound. In that table our novel softener is compared to standard commercial softening agents by showing Drape and Flex stiffness test data. Such Drape and Flex stiffness tests, performed according to Method 5206, Fed. Specification CCC-T-190l- B Stiffness of Cloth, Drape and Flex Cantalever Bending Method (Pierce.formula), are indicative of the relative effectiveness of softeners.

TABLE 2 Concentration; Flex Softener percent Drape Stiffness, (based on stillness inchtabric pounds weight) Blank. 0. 0 1.16 6.02X1O- methyl-bls-h drotallow hydrazinium chloride 0.2 1.01 3.98Xl0- Commercial Softener A 0. 2 1. 20 6. 67 10- Commercial Softener B 0. 2 1. 09 6. 03x10 In additionto their use as softeners,' our novel compounds have good detergent properties which make them .oily materials, (4) ability to peptize aggregatesof solid 70' "is'neces's'ary to prevent "soil redeposition on the surface particles and (5) ability to deflocculate or stabilize dispersed systems of solid particles. This latter property clean fabric. Ou'r novel compounds possess to a more, they may be converted to synergistically effective The products of Example III and Example IV show the same general solubility characteristics in organic solvents as does the product of Example II. However, there is a marked difierence between the analogous chloride, bromide and iodide in aqueous solutions with respect to their solubilities. The dimethylhexadecylhydrazinium chloride is water soluble and forms micelles; the bromide is slightly water dispersible; and the iodide is' water insoluble. The general preparative reaction for these analogous halides (products of Examples III and IV) is shown below in Equation 2. r i

The base available commercially as Armecn DM-18, is, according to its manufacturer, a mixture of compounds of the formula: RN (CH where R is approximately 7% hexadecyl, 90% octadecyl, and 3% octadecenyl. A 25 ml. portion of this amine (19.9 g.) dissolved in 250 ml. of xylene Was reacted with chloramine from the generator described in Example I. The reaction mixture was allowed to stand for 2 hours and then filtered. The'dried product was 24.2 g. of white solid, crude 1,1- dimethyl-l-octadecylhydrazinium chloride. This novel product was by analysis 85% pure and was obtained in 87% of the theoretical yield. On repeated recrystallization from isopropyl alcohol, it formed waxy plates that underwent a phase change at approximately 108 C., and melted with decomposition at about 160 C. Less pure samples, containing even small amounts of ammonium chloride, tend to melt at higher temperatures, often around ZOO-230 C. Our novel product is dispersible in cold water, forming soapy foaming colloidal dispersions. It is soluble cold in chloroform, dimethylformamide and Cellosolve. It is recrystallizable from ethyl and isopropyl alcohols, xylene, nitromethane and acetone. When treated with potassium hexafiuorophosphate it formed a compound which decomposed about 176 C. The preparative reaction of the novel octadecyldimethylhydrazinium chloride and the further metathesis to produce the hexofluorophosphate salt is shown below in Equation 3.

The product available commercially as Armeen DMCD is a mixture of tertiary amines of the general. formula: R-N--(CH where R is, according to the manufacturer, approximately 8% octyl, 9% decyl, 47% dodecyl, 18% tetradecyl, 8% hexadecyl, octadecyl, and 5% octadecenyl. It is prepared for sale by converting mixed cocoanut oil fatty acids to the mixed amides, dehydrating these catalytically to the nitriles, and hydro genating to give the mixed amine. The distilled, but unfractionated, primary amine mixture is then dimethylated, e.g., by the Eschweiler procedure (formic acid and formaldehyde). The tertiary amine is again distilled with' out fractionation to free it from the forerun of olefinic by-products and the non-volatile tailings.

A 400 g. portion of fArmeen DMCD, was dissolved in a mixture of 250 ml. of n-heptane and 250. m1. of dry chloroform. This solution was subjected to a chloramine gas stream from the generator of Example 1. During the course of the reaction sufiicient heptane was added to keep the volume constant. Although the reaction was exothermic, vaporization of the solvent served to keep .6... temperature relatively constant. After the reaction was completed, a liter of chloroform was added and the mixture was filtered free of ammonium chloride. Partial stripping of the solvent gave two layers which, after being chilled, were separated by decantation. The upper, darker-colored layer contained about g. of unconverted amine. The larger lower layer containing the crude hydrazinium chlorides was stripped of solvents, extracted cold with an equal volume of cyclohexane, then repeatedly washed with n-heptane. The washed oil, freed of solvent by heating first to C. at one atmosphere, then at 60 C. at 30" gage vacuum, was converted to a very soft tan paste. This material by analysis was approximately 98.5% hydrazinium chloride of the formula:

r CmHrwI r-NH, o1-

Approximately 225 g. of product were obtained by the procedure described above.

Example VII The commercial mixture, Armeen DMCD, described in Example VI was fractionally distilled through a laboratory column to get amajor fraction boiling at approximately C. at 35mm. It was refractionated, and the middle third of the cut coming over at 144 C. and 35 mm. was taken as 95% pure dimethyldodecyl amine, C H N(CH molecular weight 214, on the basis of its neutralization equivalent with standard HCl solution.

A g. portion of this purified amine was dissolved in approximately a liter of n-heptane. The solution was subjected to the chloramine ammonia gas stream at a rate of about 0.0025 mols of chloramine' per minute for about four hours. Heptane was added as necessary to restore volume. The solution was filtered; the filtrate was reacted with additional chloramine and refiltered. Solids thus obtained were extracted with chloroform and the extracts were combined. Most of the solvent was removed and'the resulting mixture was poured into approximately an equal volume (200 ml.) ofethyl acetate. A cloudy suspension of fine particles immediately resulted. The particles were removed by filtration, re-

crystallized several times from the ethyl acetate and vacuum dried to give 33 g. of off-white 1,1-dimethyl-1- dodecylhydrazinium chloride. This product was 95.8% pure by analysis. The low yield of pure product, in comparison to the hexadecyl and oc'tadecyl compounds, is due to the poor chloramination reaction. This is readily understandable, since unconverted amine can be recovered in excellent yield from the heptane mother liquor and the ethyl acetate filtrate. This resistance to chloramination of the dodecylamine is apparently a steric effect, since it. parallels the formation of macrocycles (i.e., Ruzicka and others have shown that 16- and 18-membered rings are formed in much higher yields and more readily than 10- to IZ-membered rings).

Example VIII 47.l8,- percent H 9.34, percent N 7.86, percent I 35.62;

found: Perceut'C 47.33, percent H 9.00, percent N 7.65, percent I 35.52. a

/ Example IX A 100 g. portion of tri-n-hxylamine in about 1000 ml. xylene was subjected to the chloramine stream from the generator (converting 0.06 mole chlorine/minute) for about 2% hours. The mixture was filtered and filtrate returned for additional chloramination. The cake obrained ite n the first and composition: Y

90% {ammonium chloride; The second 'filtra'te was evaporated to give a 'viscous oil, almost, pure 1,1,1-tri-n- An amine similarto thatQofExam'ple 11, available commercially as fArmeen 'DMS has the samegeneral formula (where 'R is a mixture of alkyl "and alkenyl residues derived from soybean' fatty "acids and has 'apsecond" treatment was about :proxir'n'ately the composition hexa'decyl, 17

joctadecyl, 26% octadecenyl, and 37% octadecadie'nyl). '20 of this amine 'were dissolved inSO ml. "of xylene. This solution was treated with thechlorarnineammonia gas mixture prepared by the generator described in'Example I. This reaction mixture gave as a product asolvent-insoluble tan solid meltingtat 208-240" C. .E-xtrac tion with chloroform followed byi'evaporation of this solvent and trim-ration 'with n-heptane gave purified 1,1-'diinethyl-l-soya?-hydraziniu'm chloride. This novel product appeared-as a soft tan wax which ran clear at about 140 :C. --It is a highly unsaturated salt of the general It is highly water soluble. It readily forms a hexalluorophosphate which decomposes at about --l'7'5 "C.

The actual complexity of the novel product was demonstratedfirst by preparing it in trichloroethylene' rather than xylene. Under such conditions the organic product which .pr'ecipitatesas chloramination proceeds is a mixture very largely of dimethyh'exadecyl and difiltered free of ammonium chloride, treated with an equal methyloctadecylhydraziniumchlorides. Such a material resembles very; closely the product obtained from chlorfamination of the "dimethylhexadedyl dimethyloctadecyl- Qamine vmixture available commercially as Armcen DMH However, froml the trichlorethylene reaction filtrate was obtained ahighly unsaturated, air-oxidizable pasty mixture of hydrazinium chlorides, largelythe dimethyloctadccenyl' and octadecadienylhydrazinium"chlorides. Difference in compositionyof the two fractions 'is fdmonstrated by their reaction with' iodine. ment'of chloroform solutions of the two fractions slowly at room temperatures" with half of the theoretical amount of iodine in chloroformg'ave a rapid decolorization and absorption by the unsaturated fraction resulting in the formation of a semi-sol-id mixture of ibd'oiocta'decyl and iodoo'cta'decenyl hydra-ziniu'm chlorides. The saturated fraction, however, was oxidizedby theiodine to a'large "extent, forming some amine hydroiodide, some nitrogen, and an unstable iodo compound with strong oxidizing properties,- presumably havinga nitrogen to iodine covalent bond. 7

Example XI 3 In pre-pilot plant studies, it was suggested that amore ,..,'efiicient 1procedure for making the dimethylsoyahydrazinchloride would be one in which less chlorzimi-ne was lost as ammonium chloride' -To'obtain this desirable result;itfl'was consideredi'of interest to run a limited ja'inountof chloramine into a concentrated solution of amine,filter off the cake, then make the filtrate up to its original amounts of amine and solvent forrechloramina-.

tion. The cycle wasre'p'eated until the by 'p'r'oduct build up in the filtrate made itsfus'eless efficient.

Starting with 100%? f y yamine in xylene} Treat- I chloramination was continued (,using chloramine from a 0.0061 mole per minute flowofchlorine to thoigenerator) than did the use 01E a 10% amine solution.

conversion ol-I amine; Where chloramine was used equivalentto a 71.5% conversion ofamine in a similar run, the yield of isolateii product dropped to 53.2%--

based on chloramine, the difference being due to the ammonium:*chloride'formcd. Use of a33% amine solution gavehigher zcon'versions of chlorine to product The product as originally obtained isabout 3% soluble in xylene at room temperature. Recycling, however, gives fractionation into more and less' unsaturated fractions.

I Example XII :An amineavailable commercially as Armeen M2C is approximately 34% R NQH and 5% R N, where R is approximately 8% octyl, 9%'- decyl, 47% dodecyl, 18% tetradecyl, hexadecyl, 5% octadecenyl, and 5% octadecyl. '1 he amine is a viscous yellow liquid with a combined molecular weight of 389 for the mixtureflof tertiary amines, or 136 for the overall product. The mixture of 700 g. of M20 in 2 gallons of benzenewas subjected for two and three quarter hours to a flow of 0.04 mole of chloramine per minute. 'As soon as the reaction, was completed, the mixture. was warmed slightly,

volume of heptane and evaporated. From the filtrate was obtained, after vacuum drying at C., 650 .g. of tan methyldicocohydrazinium chloride,

appeared as a soft wax which, unpurified, contained practically no' amine and. very little, ammonium chloride. Orrthe basis -of89% tertiar-y lamine "the yield obtained was 92% of theory.

Example XIII V A base commercially available as Armeen M28, a mixture largely of tertiary amines having the formula R NCH where R is soy-a (defined in Example X) was mixed in a-28 ml. quantity with 5-0 ml. "of xylene. This mixture was treated over -'a' period of ninetyminutes with a three-fold excess of chloramine. A cold water bath was used to keep the temperature down to about 40 C. during the exothermic reaction 'which ensued. When all the .chloramine was consumed the solution -wa's filtered. I The solid obtained therefrom was largely-ammonium chloride-containing about 14% product. The filtrate was evaporated to givefa brown pasty'residue, a crude 11,1-disoya 1 methylhydrazinium chloride. This 'material'wasextractedwith'ether-togive pearly tanplates of pure product which were diethylether-insoluble.

These plates were combined with the ether washed chloroform-soluble portion of=the --reaction precipitates The combinedsolids, recrystallized from ethyl acetate-either mixtures, gave pearly tan plates that on the melting point block ran clear at 158-160 C. The product was similar to that of Example X in'-that there was fractionationby *solvents 'with "less. saturated, more soluble, and more nearly saturated, less. soluble, portions.-

Example XIV i chain, derived from fihydrogenated tallow -ifatty acids,

.containing approximately 3 0% hexadecyleand 70% no tadecyliresidues. Thegcombined molecular weight of this product {is "f'calculated by its manufacturer :to be about 622. lhis'i's based on atr average aminepurity of about 89 percent. The parent amine mixture, partially dissolved in approximately twice its weight of xylen, was

treated with a chloramine-ammonia gas stream. During the chloramine addition, the base dissolved immediately,

and after a few minutes a waxy emulsion appeared in the reaction mixture. The formation of this emulsion was accompanied by a temperature rise from 30' to 73 7 C. After cooling the mixture to room temperature, it was difiicult to filter. A waxy solid was obtained by filtration after a xylene wash. The solid was a mixture of 12 parts NH Cl and 88 parts of the hydrazinium salts, chiefly methyl-bis-octadecylhydrazinium chloride,

representing 63% of the theoretical yield of the desired product. This new compound was an amorphous white wax which could be recrystallized from water. It was moderately to very soluble in chloroform and recrystallizable from many other solvents. It yielded the characteristic derivatives with KPF and KHgl The pure product ran clear at about 160 C., first showing a phase change at about 90 C. The waxy crystals of 1,1-bis-hydrotallow-l-hydrazinium chloride, described as pure, actually represent a mixture of the homologous alkyls referred to above- Chromatographic separation on analytical grade silica gel gave some resolution into the 3 major components, butthe method was tedious and unrewarding. Six recrystallizations from xylene. followed by recrystallization from water, gave a glistening white wax which analyzed very'well for l-methyl-l, l-dioctadecylhydrazinium chloride. -Calculated for C H N Cl, percrystallization from xylene gave a nearly quantitative yield of crystalline product, melting at 145-l47 C.

, Example X VI An ammonium chloride-free, amine-free portionof the unfractionated product of Example XIV was converted to the corresponding bromide by the procedure of Example III. Calculated for C H7 N Br: percent C 70.32, percent H 12.60, percent N 4.43. percent Br 12.65; found percent C 72.01, percent H 12.59, percent N 5.1 l, percent Br 12.24. The analytical results reflect the mixed nature of the hydrazinium cation.

Example VII In a similar manner the product of Example XIV was converted by the procedure of Example IV to the corresponding iodide. Calculated for C3qH-9N2I: percent C 65.45, percent H 11.73, percent N 4.13, and percent I 18.69; found percent C 66.07, percent H 11.66, percent N 4.45 and percent I 17.6.

, Example XVIII Example X V V A solution of 15.5 g. of the technical grade dialkylmethylamine described in Example XIV as Armeen MZHT" was dissolved in chloroform that had been previouslydried over magnesium sulfate and placed in a large test tube equipped with two gas inlet'tubes extending almost to its bottom, a gas outlet tube leading to Dry Ice-Dowenol traps and a thermocouple well. Solvent was added to give a head of about two inches above the bottom of the chlorine inlet tube, which in turn was slightly above the bottom of the ammonia inlet tube. Ammonia was passed through the solution for 2-3 minutes, while a very small stream of. nitrogen'was trickled through the chlorine feed line to sweep out ammonia. Chlorine equivalent to a total of'10.2 g. chloride was then bubbled in continuously over a period of 34 minutes. During this time the temperature of the reaction mixture rose from 31 C. to C., and a white solid was formed as the reaction progressed. The gases were cut 01f, and in less than thirty minutes all traces of active chlorine in the reaction medium had disappeared (as tested with an acetic acid-potassium iodide solution). The mixture of a white crystaland light yellow supernatant was filtered rapidly; the solid was washed with two m1. portions of dry chloroform. The washed and dried solid was shown by analysis to be ammonium chlooride free of hydrazinium chloride. An aliquot of the chloroform filtrate titrated for product, established the overrall yield of this reaction, based on amine, to be 83% of chemical theory. From' the chloroformfiltrate there was obtained on evaporation the crude l-methyl- 1,l-dioctadecylhydrazinium chloride (sometimes'called 1,1-dihydrotallow"-l-methylhydrazinium chloride). Re-

Example XIX A highly branched chain amine mixture available commercially as Primene JM-T is reported to be a mixture of olefinic amines of the general formula where R comprises unsaturated branched chain hydrocarbon residues of chiefiy 15-21 carbon atoms. This commercial mixture is described as having an experimentally determined neutralization equivalent of 315, a boiling range of 265-308 C. (for 570%, at 760 mm.), a specific gravity at 25 C. of 0.840 and a refractive index at 25 C. of 1.456.

A stirred mixture of 0.2 mole (6.67 g.) paraformaldehyde and 0.3 mole (15.33 g.) .of formic acid were heated to 5060 C. and at that temperature 0.1 mol (31.5 g.) of Primene JM-T was added over a period of 20 minutes. A slightly exothermic reaction ensued. The mixture was refluxed for one hour after the addition was completed and then cooled to 15-20 C. At that temperature, with good stirring, it was treated with an excess of 10% NaOH solution. 50 ml. xylene were added thereto. The upper organic layer was saturated and extracted twice with 50 ml. 1% NaOI-I solution, then twice with deionized water." This washed solution was dried over anhydrous magnesium sulfate for 2 hours. Since a small portion of the dried solution, on mixture with onehalf its volume of freshly distilled, acid-free acetic an hydride, gave less than a 1 temp. rise, the product was taken as dimethyl-Primene JM-T,

' 0. Q 1 mole per min llte' wasfstarted through the solution;

both the chlorine and ammonia were allowed to tiow'for 2 hours. After the active chloii'ne had disappeared the mixture was filtered and washed well with cold xylene. It was then treated with 230 ml. portions of hot (about 100 C.) xylene and the combined filtrates and washings were evaporated dry. Test showed the white crystalline.

residues which .were thus'obtained :to 'be almost pure ammonium chloride; The light-brown filtrate and wash on evaporation 'gave a very thick tan oil, very,v largely a solution of the' ehloramine adduct of dimethyl- Prirnene mixed with 'unreacteddimethyl Prime'ne.

Titration of small portions of the residue with's'tandardiz'ed silver nitrate solution "and 'standar'dizedHCl in isopropyl alcohol show'ed thatfth'e yield ofhydrazinium chloride (chloramine Iadduct) based on the reafcte'd "a'm'in'e was boiling petroleum ether removed all of the unreacted tertiary amineand a small, portion of the adduct, leaving a 1,I-dimethyl-i=alkylhydrazinium chloride,

:as a thi'c'k'oih; i an not'forma water-insolublepicrate or The prepafativefreactibns "for the intermediate. dinitiiyl Primenfe JM-T and thewiiovel Q A stirred dispersionofd g. of metiylbis hydrotallow hydrazinium chloride (the product of Example XIV) and 100 ml. of water at 75 C. was treated dropwise over a XVII (the bromides and iodides analogous to the p oneer of Example XIV);fai-led to produce a good yield-etp'ure product. With the hydrazinium bromide, the thio'e'yanate, relatively free of bromide, can be made to precipitate in a relatively pure state only it is run in much more dilute solutions: viz: 0.1 to 1% by weight. It is also'nece'ssary that these solutions arekept above about 60 C. since below that temperature the thiocyanate precipitate is badly contaminated by unreacted bromide. The iodide (the product of Example XVII) is not appreciably more soluble than the thiocyanate, if that soluble. Therefore,

attempts to convert the iodide to the pure'thiocyanate by the metathesis of Example XX have failed completely.

Example XXII The success of the simple metathesis reactions-described in Examples XX and XXI depend on solubilityrelation- 'sh'ips. This is likewise true for many uses "of' hy'dra- *zinium salts. For thisreason a comparative solubility (n 1,1-dimethj7l-1-hexadecyi hydrachlora'mine' aldduotareishownbelowin'Equ tions land 5.

(E) 1,1 b'is"hydrotallow l-methylstudy was made of two sets of halides. One percent'b'y :weight soligtionso'f the products of Examples ILL fill and IV, XIV, XVI, and XVII, in water were prepared at temperatures not over 7 0" C. and allowed to cool to roo'm. 7

temperature. The observations on the relative solubility of these compounds are reported below in Table 3;

. TABLE '3 commune observations Clearly soluble and transpa ent at room temperature andabove.

(A) 1,1 dimethyl 1 hexadecylhydrazinium chloride.

ziniurn. io (D) 1,1-bls"hydrotallowfd-methylhydraziuium chloride.

at room temperature. Clearly soluble at 70 0., not

at C. Fluid, opaiescent, complete tore. I i rystals undiss olvedh'nd hydrazinium bromide. undispersede en -at--C (F 1,1-his"hydrotallow l-methyl- "Many crystals 'liridissolseda Y e ;),C. le3s soluble than C or hydraziuium'iodide.

Example XXIII Theprocedure of Example XXII was substantially repeatedlusing 0.25% deionized water solutions of the six compounds listed in Table 3, at approximateiy[ 70 C;-

On being allowed towel to room temperature compounds B, C, E, and F (as designated abovein Table 3) crystallized out as platelets. Compound Aremained clearly dissolved and compound D clearly dispersed. The

practical disadvantages ofthe poor solubilitie's exhibited by compounds Eand 'F are cogently demonstrated by period of 10 minutes with asolution of 5 g. Na'SCN in 10 -ml. water. Animmediate flocculant white precipitate formed. The reaction mixturewas"cooled to'roomteme '5 pera'ture with constantstirring, filtered, washed well with waterland vacuum dr'ijed. A nearly quantitative yieldof 1,1-bis-hydrot'allow --l "methylhydra'zin'ium thio cyan'ate was obtained by. this procedure. ..The-light white product is somewhat greasy to the touch but 'le's's sothan thechloride. '-It isless soluble than' the corresponding chloride 'in water, although it appearsto be more soluble in xylene and isopropyl alcohol. It melts clear at about 6.0=C.

I and decomposes with gas evolution and "darkening 'at about 180 C. The preparative reaction l'is.shown:below inEquationfi." l r totenement-Nut][som+1-nio Attempts to prepare the hydraziniumthiocyanate ot Example XX from the products of Example XVI or the results of Example XXVI.

Example XXIV V v Equal volumes of the 0.1% solutions of compounds A, C, D, and F of Example XXII (using the designation of Table 3), were treated with 3 drops of a 10% starch dispersion and then with l ml. of hydrogen peroxide soiutionJtThe results are reported in Table 4 below.

1 TABLE '4 V Compound Observations (A) 1,i dimethyl-l-hexa'ieeylhydrazinlum chloride No discloration. C) l,l-dimethyl-l-bexadeeylhydrazinium iodide. Very dark stain. (D) 1,l-bts"hydrotallow-1-methylhydrazlnium No discoloration chloride. (F) l-i-iisi hydrotallow"-i-methylhyd.razlnium Dark stain. v

Formation of the discoloration characteristic'ofjthe iodine-starch complex is proof of "the lack of commercial I usefulness ofthe hydrazinium" iodides in the textile industry. Thus, consider a starched fiber treated with (a) first 'a hydrazinium chloride and (1;) a hydrazinium iodide. Subsequent laundering of the fibers in the pres- Ciearly soluble at 70 0., not

dispersion at room tempera ence of any common laundering oxidant,- e.g. hypo chlorite, peroxide, perborate or chloroarnide can cause oxidation of the iodide, but not the chloride, to the stainproducing starch-iodine complex. This cogent proof of the ineffectiveness of hydrazinium iodides as textile adjuvants is further supplemented by the results of EX- amples XXV and XXVI.

Example XXV As a quick practical substantiation of conclusions reached in Example XXIV pairs of white cotton fabric swatches were impregnated by padding to a 2% concentration of the following hydrazinium salts: blank (none) and compounds A, C, D, E, and F as named in Table 3, supra. These fabric swatches were air dried and separated into two sets. One set of the fabrics were retained and the other set was exposed to the action of nitrous oxide gas flowing from a cylinder at a controlled rate through a chamber in which the fabrics were suspended.

After exposure all of the fabrics were ironed with a steam iron for purposes of applying wet heat. Tensile test measurements were made on the fabric swatches. The results are shown in Table 5.

1 Yello wed excessively.

' The results in Table 5 make it increasingly obvious that while hydrazinium bromides and iodides may give some degree of protection against oxidative degradation of the cotton, only the chlorides give truly adequate protection without discoloration. Infact, the methylbishydrotallowhydrazinium chloride, the most effective textile softener among our novel compounds, actually increased the strength of the tested fiber by 6%. h The excessive yellowing of the fabrics treated with the hydrazinium iodide on steam ironing again substantiated the proposition that hydrazinium iodides were totally unsuitable for textile work.

Example XXVI bromide caused appreciable spotting of the fabric. Likewise, the iodide caused marked spotting. Only the chloride gave the same spot free fabric comparable to the blank. On the basis of this test alone it can be concluded that only the chloride is suitable for finishing dyed fabric, since spotting makes the fabric totally unacceptable to the public. The potential hazard resulting taken of each .35

Id from spotting when the hydrazinium bromides or hydrazinium iodides are used will rule them out as acceptable textile finishing agents.

Exam le XXVII To prove the superiority of our novel products as effective textile softeners cotton fabric was impregnated by the exhaustion procedure with 0.1%, 0.4% and 0.5% concentrations (based on the weight of the fabric) of the products of Examples VIII, IX and XIV. The conditioned fabrics were tested for flex stiffness by the procedure described in the specification, supra. The results of these additional standard softening tests are shown below in Table 6.

TABLE 6 Hydrazinium Salts Concentration Blank Bishvdro- Trihexyl Dodecyl tallow 207x10 0.1%.--. 1.45Xl0 1. 78X10- 1. 56X10 0.4%.-. 0. 967x10 1. 41x10" 1. 27X10 0.5% 1.. 17x10 1. 56X10' 1. 41x10 Table 6 indicates that each of hydrazinium chlorides tested showed a degree of softening effect. However, it is undeniable that the methylbishydrotallowhydraziniurn chloride is markedly superior to either of the other chlorides tested. In fact, at 0.4% concentration is showed more than improvement in softness over the blank sample. However, the choice of a commercial textile softener is predicated on considerations of a far wider and deeper kind than the objective tests shown hereabove.

Aesthetic considerations of hand, fullness and softness have long been employed by the users of textile softeners to judge the practical effectiveness of these compounds. it may be added at this point that the trihexylhydrazinium chloride tends to impart odor to the treating solution. Such an aesthetic consideration would make the use of this particular compound untenable. However, of even greater significance in textile work are detergency and defiocculation. Objective measurements of these important characteristics, which are so essential to textile adjuvants, clearly demonstrate the superiority of our novel compounds.

Example XXVIII The co-pending application of Bernard Rudner S.N. 619,691, filed November 1, 1956, discusses the use of our novel surfactant hydrazinium chlorides as valuable parts of detergent mixes. We have shown that some of our novel compounds are unexpectedly valuable detergents in themselves. To prove thisunexpected utility, the following experiment was run. Test swatches 4 X 8" were prepared by stapling 4 x 4" swatches of Foster D. Snell soiled cotton to 4 x 4" swatches of clean Indian Head cloth. The Indian Head cloth had previously been scoured and desized by washing with Renex-20 (a commercially available nonionic detergent). Test swatches, in individual Mason jars, were treated with twenty times their weight of 0.25% aqueous solutions of the four hydrazinium chlorides listed below in Table 7. The tests were run in triplicate.,..The twelve swatches were then run in an Atlas-Launder-Ometer using a 1 hour wash cycle at 140"F; 'Swat ches were rinsed free of hydrazinium chloride solution, dried at F., and ironed. Using a Gardner Automatic Photometric Unit equipped with a green filter, reflectometer readings were trio of swatches and averaged. The results are shownin'l'able 7.

latter compounds have commercial potential as textile j adjuvants.

Detergency is aprimary attribute of compounds which mega? are useful in the textileindustry. The objective data of Table 7 is a synergistic measurement of (,1) preferential wetting, (2) dispersion, (3) deflocculation and (4) emulf sification. It has been previously indicated that a surfaceactive compound must posess each of these properties in order. to be an effective detergent. The usefulness of a surface active compound as a detergent is. limited by the poorest of 1 these four properties The first of these, preferential wetting, is equally important in the selection of a softener. 'Like detergency, eifectivesoftening de mands uniformity. -Uniforrh'ity of softening is only obtained through a high degree of wetting and spreading on the fabric. Drape and. Flex tests are not necessarily conclusive as to the uniformity of softening of thetabric.

It is truethat Table .7 cannot beused todemonstrate preferential wetting'alone: The combined effects ofdispersion, defiocculation and emulsification. maywell mask this particular property. Table 7 cogen-tly showsa marked difference in kind and not merely in degree between the compounds of short carbon chain such as'the .dimethyldodecylhydrazinium chloride and those having longer carbon chain's such as the dimethylhexadecylhydrazinium chloride. Only these Eirample XXIX, Using the standard dilution technique, aqueous solutions of the hydrazinium salts of Examples 11, III, IV,

VII and VIII were inoculated with a 4 mm. loop of actively growing 24 hour old Difco infusion broth cultures of micrococcus pyrogenes var. aureus. These cultures were incubated at 37 C. for 48 hours and then examined microscopically for colonies. Once bracketing dilutions were found, additional dilutions were" made to obtain the minimum inhibitory concentration. As a control, the commercially important'quaternary ammonium antiseptic agent" Zephi'ran was used". Results appear in I Tabledbelo'w: v

TABLE s Bacteribstatic effects Minimum Compound Inhibitorv Concentration Dimethvlhexadecylhydrazinium chloride 1:46, 000 Zephiran 1:36. 000 Dimethylhexadec lhydrazinium iodide 1:35, 000 Dimethylhexadec lh dra zinium bromide. 1:32. 000 Dimethvldodec"lhydrazinium chl0ride 1:30, 000 Dimethyldodeeylhydrazinium iodide- 1:1, 000

Thus is can be seen that our novel dimethylhexadecylhydrazinium chloride is not only more effective than the known hydrazinium chlorides, bromides or iodides, but it;

is even 12% stronger than one of the standard commercial bacteriostats.

. Non obstant this possibility,

*ments of static propensity tested for their anti-static eifect on hydrophobic'fibers. Samples of a Dacron fiber were impregnated by the padding technique with 0.4% by weight based on the weight of the fiber of the three hydrazinium salts. Measurewere made at 30% RH, 40% RH, and 50% RH.

TABLE 9 ANTI-STATIC PROPERTIES ["Dacron" fiber impregnated with 0.4% by weight of hydrazinium salt.]

Percent Relative Humidity Hydrazinium Salt Eexadecvld'imethyl chloride .J 0 0 0 Hexadec ldimethvl bromide. 66 32 0 Hexadecyldimethyl iodide 40 20 0 Table 9 shows that the hexadecyldimethylhydrazinium chloride is astonishingly useful as an anti-static agent, since at. the humidities'tested it showed no static propensity. This difference between the chloride and the corresponding bromide and iodide with relation to anti;

Weight Percent on Fibre Hydrazinium Salt' Hexadecyldimethyl chloride." 0 2 0 Q I 0 Hexadeeyldimethrl bromide 84 78 38 14 Hexadeoyldimethyliodide-.. 46 24 12 30 i 20 Example XXXII The hydrazinium halides of Examples II, Ill and IV, were tested for their ability to function as dispersing or defioccula'ting, agents. A device was constructed consisting' of an optically clear sample holder enclosed in a light- .tight housing, a source of constant intensity, a photonic cell, and microammeter. Light transmission through solutions containing the compound to be tested in known concentrations and dispersed or suspended carbon black is measured at regular time intervals and the amount of light transmitted through the dispersion is indicated by the intensity of the current generated by the photonic cell. The current intensity is observed in microamperes and recorded. The instrument is standardized so that water contained in the same sample holder had a transmission of 100 microamperes. 100 cc. of solution containing 0.1% carbon black and 1% of the compound selected for testing were prepared and transmission was measured immediately after preparation. The remaining solution was allowed to stand in a 100 cc. graduate and after 10. minutes a sample was pipetted from the middle of the remaining solution. Transmission measurements were again made. At 10 minute intervals samples were taken until four readings Wereobtained. The results of these tests appear in Table 11.

19 TABLE 11 DISPERSION AND DEFLOCCULATION PROPERTIES Reading in Microarnperes Hydrazinium Salt Initial After After After After min. 20 min. min. min.

Hexadecyldimcthyl chloride. 34 42 44 47. 5 46. 5 Hexadeeyldimethyl bromide. 42. 5 57 60 72 75 Hexadeerldim ethyl iodide 64 74 78 82 Carbon black only p 45 54 70 72 79. 5

corresponding analogous halides are suitable as textile adjuvants. First, of the halides only the chloride possesses the desirable solubility characteristics of complete solution and dispersion. Second, the chlorides show. pronounced advantage over the iodides in that they form no colored complex when oxidized in the presence of starch. That the dark stains resulting from the formation of an iodine complex on the surfaces of a starched fiber are undesirable is too obvious to be labored at great length. Third, the hydrazinium chlorides do not appear to impair the tensile strength of cotton fabrics treated with these salts and exposed to acid oxidation influences. This same desirable property does not obtain for the corresponding bromides and iodides. The iodides show considerable yellowing after steam ironing. Fourth, the chlorides seem to be especially effective for treating dyed fabrics. They have better wetting and spreading ability, and moreover because of their solubility after steam ironing they show no spotting or specking of the fabric surface. The corresponding bromides and iodides are unfortunately subject to this undesirable result. The data given in the specification, strongly supplemented by the results of Example XXVII, show that the methylbishydrotallowhydrazinium chloride is one of the most remarkable softening agents known. The objective Drape and Flex tests show the marked superiority of this compound, although they give no indication of the even more important aesthetic considerations upon which the commercial success of this specific chloride will be predicated. The higher molecular weight chlorides possess superior wetting and spreading ability which aids considerably in imparting to a fabric a uniform softness after treatment. This'uniform spreading and wetting does not readily obtain'with the lower molecular weight chlorides. Moreover, none of these latter compounds impart the plump and fluffy hand to the textiles after treatment. Example XXVlll clearly demonstrates that only the longer chain hydrazinium chlorides (viz: those having at least one aliphatic hydrocarbon chain of 16 or more carbon atoms) are effective detergents. Detergency is an important consideration in the selection of a textile adjuvant. In this respect the shorter chain chlorides are unsuitable for textile applications. The anti-static tests on the hydrophobic fiber Dacron, show in a completely unpredictable manner that the dimethylhexadecylhydrazinium chloride is astonishingly effective as an anti-static agent. Examples XXX and XXXI clearly demonstrate this unobvious and most useful property. This same compound in Example XXIX is shown to be unexpectedly eifective in its bacteriostatic effect on micrococcus pyrogenes var. aureus. When compared to a known commercial standard it alone, of the compounds tested, showed superior bacteriastatic property. Such a property is of more than nominal value in an agent used for textile cleansing purposes as well as for other diverse applications.

The foregoing test data clearly shows that of aliphatic hydrazinium halides only the chlorides embraced by the present invention have utility as textile adjuvants. The softening properties imparted to a fabric by the methylbishydrotallowhydrazinium chloride make this compound superior to the members of its class for this particular use. The dimethylnexadecylhydrazinium chloride showed unobvious anti-static and bacteriostatic properties.

We claim:

1. Compounds having the general formula wherein R is an alkyl radical having from 16 to 24 carbon atoms and R and R are alkyl radicals having from 1 to 24 carbon atoms.

2. Compounds having the general formula wherein R is an alkenyl radical having from 16 to 14 carbon atoms and R and R" are alkyl radicals having from 1 to 24 carbon atoms.

3. Compounds having the general formula References Cited in the file of this patent Westphal: Ber. Deut. Chem., vol. 74, pp. 759-776, 1365-72 (1941).

Omietanski et al.:

JACS., vol. 78, pp. 1211-13 (Mar. 20, 1956).

UNITED STATES PATENT OFF ICE CERTIFICATE OF CORRECTION Patent No. v 2,929,347 I March 22', 1960,

Bernard Rudner et ale I It is hereby certified that error appears in the printed specification of the above numberedpatent requiring correction and that the said Letters Patent should readz-as corrected below.

Column 6, line 13, after "-5 g, of" insert chloramine in a column 10, line 60, for "acetate-either" read acetateether column 11, line 2, for "xylen" read xylene column 13, lines 70 and 71, right-hand portion of Equation (6) should appear as shown below instead of as in the patent:

column 14, TABLE 3, second column thereof, third line from bottom, for "a" read at same column 14, TABLE 4, second column thereof, first line, for '"discloration" read discoloration Signed and sealed this 22nd day of November 1960.,

(SEAL) Attest:

KARL H. AXLINE ROBERT C. WATSON Attesting Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE or conaEcTIoN Patent No. 2,929,847 March 22 1960 Bernard Rudner et al0 Q It is hereby certified that error appears in the printed specification of the above numbered'patent requiring correction and that the said Letters Patent should read: as corrected below. I

Column 6, line 13, after "-5 g, of" insert chloramine in a column 10, line 60, for "acetate-either" read acetateether column 11, line 2, for :xylen" read xylene column 13, lines 70 and 71, right-hand portion of Equation (6) should appear as shown below instead of as in the patent:

column 14, TABLE 3, second column thereof, third line from bottom, for a read at same column 14, TABLE 4, second column thereof, first line, for "'discloration" read discoloration Signed and sealed this 22nd day of November 1960,

(SEAL) Attest:

KARL H, AXLINE ROBERT C, WATSON Attesting Officer Commissioner of Patents 

1. COMPOUND HAVING THE GENERAL FORMULA 